Azo derivatives of amino diphenylamines



Patented Jan. 1, 1946 STATES; PATENT OFFICE poration of Maine No Drawing. Application July 3, 1M4, .SeriaLNo. 543,431.

6 Claims. (Cl. ZINE-1773' This invention'relatesto a new series: ofazo dyestuffs derived from glycol derivatives having the following formula:

' OONH-jr-ONER, G/ V v OONHONH: in which G is the residue of a glycol having not less than two and not more than four carbon atoms.

In the past there has been a demand for icecolor having strong blue to violet shades. Many attempts have. been made to produce such dyestuffs and in many cases the-fastness properties such as "fastness to light, heat. and washing have left much to be desired. It is an advanta e f the present invention that-ice-colors. of strong blue to violet shades can be produced which as pigments or dyes exhibit superior fastness properties such as iastness to light, heat and washing. The presentinventionis not limitedto icecolors-asthe glycol derivatives-may be diazoti'zed andcoupled with other coupling components-to ive azo dyes of different shades, and dyes" which are soluble in-water and capable of, dyeingibasic nitrogenous fibers; 'Iheice-colorsproducible ;by the. present invention are particularlyoutstanding, in their propertiesand. therefore constitute the preferred embodiment of the present invention.

The. present invention is, of course, not con.- cerned with the method by which the glycol derivatives are produced. These compounds and a process of making them form the subject matter of 'ourj'copending application Serial No; 543,428 filed July 3, 1944. In general, they maybe prepared' by reacting 4 -hydroxy-4-nltro diphenylamine or its 2-sulfonic acid derivative with an ester of the glycol desired in .strongly alkaline medium followed bythe reduction :of the ,nitro groups. If the reduction. takes placein the :acid

:medium, salts of the base with the acid; are obtained and these salts are usable in producing the azo dyestuffs of the present invention.

The dyestufis or the-present invention may be made from derivatives :ofany of th ,glycols having not less;than-. two and not more. than .four carbon atoms such as ethylene, propylene, 2- methyl propylene,1-methyl propylene, l-ethylethylene, butylene glycols, diethylene .glycol, .thiodiglycol, and the sulfoxides and thesulfones derived therefrom. The shade does not differ very greatly with the different g-lycols and -be-.-.-

cause ethylene glycol. esters are considerably cheaper and .more, readily available; the azo. dyestufis derived from them are preferred.

For the. process, of diazotization, higher terns,- perature, greater; concentration of the-.base and higher mineral and:;nitrous=, acid. concentrations tend to produce; N-nitroso derivatives ofthe-:diazonium salts. Itis, therefore, in general preferable to useglower temperature, lower .aeid comicentration; and slower addition of nitritein order 'toprevent production of thenitroso derivatives as this product gi-ves duller and .lessdesirable hades on coupling.v It is possible to hydrolyze; the dyestuffs in. dilute solution by, heating w tlralk al-is, such as soda-ash. If desired, reduceing agents such as sodium. sulfide, or sodiumbi-v sul-fi-te and the like may be included in. the hyrolysis. step in order to, destroy nitric oxides. .as they are liberated.

.In their. diazotized' form, the bases may be coupled either with or without a substrate, to yield dyestuffs or pigments of great'value because of their strength, variety of shade and fastness properties; Inpartieulan-however, the base of the present invention areimpor-tant for the-pro duction of fast blue prints or' dyeings upon cellulosic materials. These are producedzin general, :byaimpregnatingxthe cellulosicrmaterialina alkabathszwithpappropriate icercolor coupling ,componentsand themprinting; solutions of the 1 diazotizedbases -.which-. have been buffered and thickened-upon .such prepared cloth, or.by pad dyemg, the prepared, cloth. buffered. solutions of thediazotizedloases.

Solutions of the diazotized bases used inthe present invention may also be treated With-inorganic alkali metal salts or-alkaline-earth" metal salts; jormixtures of these salts together with appropriateinorganic metal saltswhereupon the diazonium salts :or metal salt. complexesof the diazonium salts are precipitated. These may he; separated dried stored or blended: with winorganic :saltsrsuch for example r potassium chlorides, sulfates, magnesium sulfate, aluminum sulfate and the like; the latter prefer- :abl-ybeing, used. in their partially dehydrated forms. Such products ,may 'be' readily dissolved linwaterjto yield solutions from which cellulosic materials which have previously "beenimpregnated in alkaline grounding baths with appropriate ice-color coupling-components may be suitablypad dyed, or the solutions may lie-appropriately thickened and printed upon the prepared cellulosic fabrics.

Thetbases used in' the present invention may also be converted into diazosulfoniates which may be isolated from solution, dried, stored or they may be blended in the dry state with appropriate ice-color coupling components and oxidizing agents. Such blends maybe incorporated into a i printing paste, printed upon vegetable fibres and the pigment developed by treatment with steam.

In a reaction vessel 34.8 parts potassium 4'"- hydroxy-4 nitrodiphenylamine-2-sulfonate, 6.2 parts potassium hydroxide dissolved in 100 parts 1 of water, and 18.5 parts ethylene bis-p-toluene- 'Substantially any of the ice-color coupling":

components are generally useful for production w of insoluble, developed dyes, and enable the pro- V duction of a variety of colors from yellow to blue,

, However, for the present purposes, the use of arylids of Z-hydroxy-B-naphthoicacid is prefe v able. These produce, when coupled with the dia zotized bases used in the present invention, the

V most desirable blue to violet shades. c

However, the invention is not necessarily so limited. Among other ice-color coupling components which produce useful products may be J listed by way of examplesuchcompounds as beta-naphthol; 8-r-amino-2-naphthol, 8-acetylamino-2-naphthol, benoyl naphthols; pyrazolones and pyrazyl pyr'azolones; hydroxybenzoflourenenones; hydroxy derivatives of phenyl I naphthylamines such as 7 -hydroXy-1-naphthylm hydroxy'phenylamine; the various N-substi- 1 tutedamideS such as arylides, of 5, 6, 7, 8-tetrahydro 2-hydroXy-'3-naphthoic acid, of 2-'hy- 'droxy -3-anthroic acid, of methyl and 'dimethyl i salicyclic acids, of hydroxy carbazole carboxylic and the like. The arylide group in the coupling'component may be a, simple aromatic group such asthe radical oi aniline or of an aniline derivative or of a naphthylamine, or it may bethe radical of a heterocyclic amine, such as, e. g., of

an amine of the benzothiazole series or of a diaminei ofthe diphenylene diphenylene oxide or .diphenylenesulfone series. 1 The bases ofthe'prese'nt invention used' in the preparation of water-soluble dye- '"s'tufis' suitable for dyeing vegetable oranimal fibers. In this case,'a great many of the cus- V tomary phenolic or aminic coupling components [may beused. The coupling component, .however, 1 must carry at least one sulfonic group, in case jthediazo component has none. Illustrative ex- 'amples of ,such coupling components include salicyclic acid, resorcinol, m-phenylene diamine,

, the large number. of naphthol-sulfonic acids, such nas.e.'g.,-R acid, G acid, the Cleves acids, J acid,

gamma acid, J-acid urea andJ' acid imide, H- acid and many others. Pyrazolones such as sulfonic-derivatives of 1-phenyl-3-methyl pyrazo- Ylone-5 also may be used. i

j The invention will be'more fully illustrated in 1 "conjunction with the following examples which are 'neantito be illustrative only and notby way offlimitation. .'All parts are by weight unless otherwise noted.

2. 156 may be I 7 Example 1 V NQN bis (4 -nitrophenyl) -4,4'-aminophenyl ethylene ether sulfon ate" are'heated under gentlerefiux for six hours. After a short time; the solution becomes ;opaque and a solid starts separating; the solid (3011131111168 to increase in amount during refluxing. The reaction-mixture is chilled, and the'yellow solid is collected on a filter anddried. The crude dipotassium salt of N, N'-bis-(4-nitro-- 2," sulfophenyl)'-4,4-aminophenyl ethylene glycol ,ether'is purified by being salted with potassiuinchloride from'a hot aqueous solution.

A slurry of 36.1 parts of this dipotassium salt in 42 8 parts" concentrated hydrochloric acid is V V heated under reflux for 19 hours. During this time, the slurry changes in color from a bright lemon yellow to an orange. After refluxing, the reaction mixture is V poured into. 1,000 parts of water, and. the undis'solved solid is collected on a filter. This solid is washed free'of acid on the filter with water, and is dried.- This crude product is extracted with acetone, and.N,N'-bis-(4"- j nitrophenyl)-4,4 aminophenyl ethylene glycol ether is reprecipitated from the acetone by addition of water. Ylfhen further purified by recrystallization from dilute dioxane, ,it melts. at 184-'185?.C. f

Example 2 'l y j nei sq si ss Ns..solfi font-0 HONHLHOI 12 parts of N,N'-bis-(4" aminopheny1-4A aminophenyl) ethylene glycol ether are stirredin 136 parts of glacialacetic acid and heated to .0. A solution of-4l.5 parts of stannous chloride vdihydrate in 149. partsv .of-,concentratedhydro; Lchlo'ric acid is gradually addedovera period of time.) The reductionis allowed to p'roceedat a temperature o f"70- 0 C. for 3 hours at which is added until the slurryisacidic to Congo Red test paper: On heatingythe solid dissolves, charcoalis added; and the solution is filtered. On chilling the filtrate; N,N -bis-(4' -aminophenyl) -4,4 aminophenyl ethylene ether dihydrochloride crystallizes out. It is collected-on a filter and dried in a dessicator. I Itfis purified by recrystallization-from dilute hydrochloric acid.

Examples v A slurry oi fi parts' of-N,-N'-bis-(4"-ami nophenyl-4,4 -aminophenyl) ethylene glycolether particular ice-color coupling: component. takenin the alkaline grounding bathtareflistedibelow:

. aliiydrbiy a-ha mnoie acid amine--. 2-hydroxye3-naphthoicacid (Q'methyl mats a maethenyn; 4;4"-'-a propylene glycolether 3 propylene glycol ether is obtained as an orangeyellow' solid. 30

(4' -aminophenyl) -4,4'-aminophenyl 1 glycol ether as prepared'i n Ex'ample 8 are stirred in a solution of 5 parts of 17% hydrochloric acid and 5 parts of water at 15 C. To this is added ffollowing' shades:

' 1 'lce color couplingcomponent Bis-(acetoaceticko-tohdme Brown. T

, amaze:

. LHrOONHONOi i The procedure of Example 1 was followedex cept that 19.2 parts ofpropylene glycoLdi-ptoluene sulfonate was used insteadof 185 parts of ethylene glycol di-p-toluene sulfonate. The

"We claim: 7 .An azo dyestufi ofthe general formula: v

' "A- =N-B-'-NY='N -AV in which A is a residue" of a coupling component and B is selected from the group of glycol de rivatives of the formula; v 7

N,N' bis 4 nitrophenyl) 4,4'-aminophenyl N,N' bis-14" aminophenyl) 4,4 aminophenyl propylene glycol ether 7 i CHz-CH-OONHONEMHQI JH o-ONH-Qiwmnm The procedure of Example 2 was followed substituting the product of Example 7 for the product of Example 1. N,N'-bis-.(4"-aminophenyl)- 4,4-aminophenyl propylene glycol ether is obtained in pure form.

1.3 parts of the dihydrochloride or N,N'-bispropylene slowly a solution of 0.42 part of sodium nitrite in 5 parts of water.' The resulting solution is clarified and the filtrate is diluted to 400 parts by volume. This solution is divided in two equal portions and to each portion is added 20% sodiurn acetate solution until the solution is no longer acid to Congo Red test paper. v

7 Cotton piece goods areseparately impregnated in alkaline grounding baths by; the procedure :giescribed in Examplef4with the an ilide of 2- hydroxy-3-na'phthoic acid and with the beta:

.naphthylamide of 2-hydroxy-3-n aphthoic;acid.

5 parts .of the impregnated fabrics are separately dyed in the buffered diazo baths prepared as described above. When Tcolor development is complete the goods are finished by theprooedure of Example 4. The

goods are dyed strongly the Coupling component j j Color 2-hydroxy- 3-naphthoic acidbetanaptithylariiidejl Heavy blue.

"Reddish' blue. I

in which G is the radical'of a glycol having not less than two and notmore than four carbon atoms and their sulfonic acid derivatives, and

and their sulfonic acid derivatives, and in which the azo groups are attached to the points X. I

3. Ice-colors having the following formula;

in which A. is the residue of an ice color coupling component and B is a glycol derivative having the formula:

tgag f @WQ in which G is a radical of a glycol havingnot less than two and not more than four carbon. atoms and their sulfonic acid derivatives, and'in which the azo groups are attached to the points X.

4. An ice-color having the following formula;

in which A is a residue of ice-color coupling component.

5. An ice-color having the following formula:

in which Am'is the residue of van'arylide rof 2- hydroxy-3-naphthoic acid, andG is theradical of'a glycol having not less than 2 and not more than 4v carbonatoms. g; it

6. An ice-:color 7 having the. following formula in whichAm i the residue of an 'arynde of-"2- hydroxy-3-naphthoic acid. v

' 7 5 R BERTYVPUPAREERQ JOHN J. BENTON-V". 

